Catalytic gas phase fluorination

ABSTRACT

The present invention relates to a fluorination process, comprising:
         an activation stage comprising contacting a fluorination catalyst with to an oxidizing agent-containing gas flow for at least one hour; and   at least one reaction stage comprising reacting a chlorinated compound with hydrogen fluoride in gas phase in the presence of the fluorination catalyst, so as to produce a fluorinated compound.

FIELD OF THE INVENTION

The present invention relates to the gas phase catalyzed fluorination ofa chlorinated compound to a fluorinated compound using hydrogen fluoride(HF), and notably the gas phase catalyzed fluorination of2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf) or of1,1,1,2,3-pentachloropropane to produce 2,2,2,3-tetrafluoropropene(HFO-1234yf).

The products obtained owing to the invention, such as HFO-1234yf, areknown to have utility as a foam blowing agent, refrigerant, aerosolpropellant, heat transfer media, fire extinguisher, etc. HFO-1234yf isalso known to have zero Ozone Depletion Potential (ODP) and a very lowGlobal Warming Potential (GWP) of much less than 150.

BACKGROUND OF THE INVENTION

The Montreal Protocol for the protection of the ozone layer mandated thephase out of the use of chlorofluorocarbons (CFCs). Materials friendlierto the ozone layer, such as hydrofluorocarbons (HFCs), e.g. HFC-134a,replaced chlorofluorocarbons. The latter compounds have proven to begreenhouse gases, causing global warming. They were regulated by theKyoto Protocol on Climate Change. With the continued concern over globalclimate change there is an increasing need to develop technologies toreplace those with high ozone depletion potential (ODP) and high globalwarming potential (GWP). Though hydrofluorocarbons (HFCs), beingnon-ozone depleting compounds, have been identified as alternatives tochlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) assolvents, cleaning agents and heat transfer fluids, they still tend tohave significant GWP. Hydrofluoroolefins (HFO) have been identified aspotential alternatives with zero ODP and low GWP.

Hence, numerous documents teach processes for making such HFOs,including HFO-1234yf.

For example, WO 2007/079431 discloses processes for the production offluorinated olefins, including hydrofluoropropenes. The processes whichare broadly described as a single reaction or two or more reactionsinvolve fluorination of a compound of the formulaC(X)_(m)CCl(Y)_(n)C(X)_(m) to at least one compound of formulaCF₃CF═CHZ, where each X, Y and Z is independently H, F, Cl, I or Br andeach m is independently 1, 2 or 3 and n is 0 or 1. HFO-1234yf isprepared by fluorinating HFCO-1233xf into1,1,1,2-tetrafluoro-2-chloropropane (HCFC-244bb), followed bydehydrochlorination. HFCO-1233xf is prepared by fluorination of thecorresponding chlorinated precursor (CCl₂═CClCH₂Cl).

EP-A-939071 discloses, among many possibilities, gas-phase fluorinationof a halogenated propene (according to a very long list) into afluorinated propene (including in the list HFO-1234yf).

WO 2008/054781 discloses a variety of processes for producing a varietyof fluoropropanes and halofluoropropenes by reacting halopropanes orhalopropenes with HF, optionally in the presence of a catalyst. Itdiscloses a process for making HFO-1234yf by reacting2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) in the presence of HF,on a catalyst, especially Cr/Co (98/2). Reaction products compriseHFO-1234yf and HFCO-1233xf, the latter being the main product; otherproducts are 1-chloro-3,3,3-trifluoro-1-propene (HFCO-1233zd) as well as1,1,1,2,2-pentafluoropropane (HFC-245cb) and1,3,3,3-tetrafluoro-1-propene (HFO-1234ze).

WO 2008/002500 discloses a process for making a mixture of HFO-1234yfand HFO-1234ze by catalytic conversion of 1,1,1,2,3-pentafluoropropane(HFC-245eb) on a dehydrofluorination catalyst.

WO 2008/040969 discloses a process comprising dehydrochlorination ofHCFC-243db into HFCO-1233 (xf as well as zd), followed by a reactioninvolving formation of 1,1,1,2-tetrafluoro-2-chloropropane (HCFC-244bb)and later formation of the desired HFO-1234yf throughdehydrochlorination. Example 1 of said document discloses a gas phasereaction at atmospheric pressure of HCFC-243db with HF on a Zn/chromiacatalyst, whereby HFO-1234yf and HFCO-1233xf are formed, together with asmall amount of HFC-245cb.

WO 2009/015317 discloses the reaction of a chlorinated compound whichcan be 1,1,2,3-tetrachloro-1-propene (HCO-1230xa),1,1,1,2,3-pentachloropropane (HCC-240db) or2,3,3,3-tetrachloro-1-propene (HCO-1230xf) with HF, in gas phase, on acatalyst and in the presence of at least one stabilizer. This processmakes it possible to obtain 2-chloro-3,3,3-trifluoro-1-propene(HFCO-1233xf).

US 2009/0240090 discloses a process for making2,3,3,3-tetrafluoro-1-propene (HFO-1234yf) starting from a compound offormula (I) CX₂═CClCH₂X, or formula (II) CX₃CCl═CH₂ or formula (III)CX₃CHClCH₂X with X═F, Cl, Br, I. The process comprises three steps,which can be followed by purification. The process includes recyclingsteps allowing higher conversions and yields.

WO 2010/123154 is directed to a process for producing HFO-1234yfstarting from HFCO-1233xf, by reacting it with HF in the presence ofoxygen and a catalyst comprising chromium oxide or fluorinated chromiumoxide.

However, there is still a need to provide an improved process for makingfluoroolefins such as HFO-1234yf, having in particular an improvedconversion rate and/or an improved selectivity and/or which is effectiveover a longer period of time.

SUMMARY OF THE INVENTION

The present invention provides a fluorination process, comprising:

-   -   an activation stage comprising contacting a fluorination        catalyst with an oxidizing agent-containing gas flow for at        least one hour; and    -   at least one reaction stage comprising reacting a chlorinated        compound with hydrogen fluoride in gas phase in the presence of        the fluorination catalyst, so as to produce a fluorinated        compound.

According to one embodiment, the process comprises a plurality ofreaction stages alternating with a plurality of regeneration stages,wherein the reaction stages comprise reacting the chlorinated compoundwith hydrogen fluoride in gas phase in the presence of the fluorinationcatalyst, and the regeneration stages comprise contacting thefluorination catalyst with an oxidizing agent-containing gas flow.

According to one embodiment, the oxidizing agent-containing gas flow ofthe activation stage and/or the regeneration stages is anoxygen-containing gas flow.

According to one embodiment, the activation stage and/or theregeneration stages comprise contacting the fluorination catalyst withthe oxidizing agent-containing gas flow for at least 2 hours, preferablyfor at least 4 hours, more preferably for at least 10 hours, and evenmore preferably for at least 15 hours.

According to one embodiment, the oxidizing agent-containing gas flow ofthe activation stage and/or the regeneration stages contains hydrogenfluoride in addition to the oxidizing agent, and the proportion ofoxidizing agent in the oxidizing agent-containing gas flow of theactivation stage and/or the regeneration stages is preferably from 2 to98 mol %, and more preferably from 5 to 50 mol %, relative to the totalamount oxidizing agent and hydrogen fluoride.

According to one embodiment, the oxidizing agent-containing gas flow ofthe activation stage and/or the regeneration stages does not containhydrogen fluoride, and preferably is air.

According to one embodiment, the activation stage and/or theregeneration stages comprise contacting the fluorination catalyst with ahydrogen fluoride gas flow, either:

-   -   before contacting the fluorination catalyst with the oxidizing        agent-containing gas flow; or    -   after contacting the fluorination catalyst with the oxidizing        agent-containing gas flow.

According to one embodiment, the activation stage comprises apreliminary step of reacting the chlorinated compound with hydrogenfluoride in gas phase in the presence of the fluorination catalyst,prior to contacting the chlorinated compound with the oxidizingagent-containing gas flow.

According to one embodiment, the oxidizing agent-containing gas flow iscontacted with the fluorination catalyst during the activation stageand/or the regeneration stages at a temperature of from 250 to 500° C.,preferably from 300 to 400° C., more preferably from 350 to 380° C.

According to one embodiment, the fluorinated compound is a fluoroolefin,preferably a fluoropropene, and more preferably2,3,3,3-tetrafluoro-1-propene.

According to one embodiment, the chlorinated compound is selected fromhydrochlorocarbons, hydrochlorofluorocarbons andhydrochlorofluoroolefins, and is preferably selected from2-chloro-3,3,3-trifluoro-1-propene, 1,1,1,2,3-pentachloropropane,1,1,2,2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane,2,3,3,3-tetrachloro-1-propene and 1,1,2,3 tetrachloro-1-propene, and ismore preferably 2-chloro-3,3,3-trifluoro-1-propene. According to oneembodiment, the fluorination catalyst is a supported catalyst, and ispreferably supported on a support selected from fluorinated alumina,fluorinated chromia, fluorinated activated carbon or graphite carbon.

According to one embodiment, the fluorination catalyst is an unsupportedcatalyst.

According to one embodiment, the fluorination catalyst further comprisesa co-catalyst selected from Co, Zn, Mn, Mg, V, Mo, Te, Nb, Sb, Ta, P, Nior mixtures thereof, preferably Ni, and said co-catalyst is preferablypresent in an amount from about 1-10 wt % of said fluorination catalyst.

According to one embodiment, the fluorination catalyst is a mixedchromium/nickel catalyst, the atomic ratio of nickel to chromium beingpreferably from 0.5 to 2 and more preferably approximately 1.

According to one embodiment, the molar ratio of hydrogen fluoride to2-chloro-3,3,3-trifluoro-1-propene is from 3:1 to 150:1, preferably 4:1to 70:1, more preferably 5:1 to 50:1, and even more preferably from 10:1to 30:1.

According to one embodiment, the reaction stages are carried out at apressure of from 1 to 20 bars, preferably from 5 to 15 bars, morepreferably from 7 to 10 bars.

According to one embodiment, the reaction stages are carried out at atemperature of from 200 to 450° C., preferably from 3 00 to 430° C.,more preferably from 320 to 420° C. and even more preferably from 340 to380° C.

According to one embodiment, the contact time between hydrogen fluorideand the chlorinated compound during the reaction stages is from 6 to 100s, preferably from 10 to 80 s, more preferably from 15 to 50 s.

According to one embodiment, the reaction stages are carried out in thepresence of an oxidizing agent such as oxygen, the ratio of oxygen beingpreferably from 0.05 to 15 mole %, more preferably from 0.5 to 10 mole%, and most preferably from 5 to 10 mole %, with respect to the totalamount of chlorinated compound and oxygen.

The present invention fulfils the need expressed in the prior art. Inparticular, it provides an improved process for making fluoroolefinssuch as HFO-1234yf.

For instance, the conversion rate of HFCO-1233xf is improved relative tothe teaching of WO 2010/123154.

The above results are made possible owing to the surprising finding madeby the present inventors that the performances of the reaction areincreased when the fluorination catalyst is activated in the presence ofan oxidizing agent such as oxygen.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The invention will now be described in more detail without limitation inthe following description.

As used herein, percentages are by molar percent unless specifiedotherwise.

Fluorination Reaction

In the fluorination reaction of the invention, a chlorinated compound isconverted to a fluorinated compound through a reaction with hydrogenfluoride (HF) in the presence of a catalyst.

The “chlorinated compound” can be any molecule having a chlorine atom,and the “fluorinated compound” can be any molecule having a fluorineatom.

Preferably, the chlorinated compound is a C2 or C3 or C4 or C5 alkane oralkene compound, which is linear or branched (preferably linear), havingone or more substituents selected from F, Cl, I and Br (preferably fromF and Cl), at least one of the substituents being Cl.

Preferably, the fluorinated compound is a C2 or C3 or C4 or C5 alkane oralkene compound (preferably alkene), which is linear or branched(preferably linear), having one or more substituents selected from F,Cl, I and Br (preferably from F and Cl), at least one of thesubstituents being F.

More preferably, the chlorinated compound is a C3 alkane or alkenecompound having one or more substituents selected from F, Cl, I and Br(preferably F and Cl), at least one of the substituents being Cl; andthe fluorinated compound is a C3 alkene compound having one or moresubstituents selected from F, Cl, I and Br (preferably F and Cl), atleast one of the substituents being F.

Alternatively, the chlorinated compound can be a C4 alkane or alkenecompound having one or more substituents selected from F, Cl, I and Br(preferably F and Cl), at least one of the substituents being Cl; andthe fluorinated compound is a C4 alkene compound having one or moresubstituents selected from F, Cl, I and Br (preferably F and Cl), atleast one of the substituents being F.

According to one embodiment, the fluorinated compound is ahydrofluorolefin (and thus has no chlorine substituent).

Preferably, during the reaction, at least one Cl substituent in thechlorinated compound is replaced by an F substituent.

The conversion of the chlorinated compound to the fluorinated compoundcomprises direct conversion (i.e. in a single reaction step or underessentially one set of reaction conditions) and indirect conversion(i.e. through two or more reaction steps or using more than one singleset of reaction conditions).

Most preferred fluorination reactions are the following:

-   2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf) to    2,3,3,3-tetrafluoro-1-propene (HFO-1234yf),-   1,1,1,2,3-pentachloropropane (HCC-240db) to    2,3,3,3-tetrafluoro-1-propene (HFO-1234yf),-   1,1,2,2,3-pentachloropropane (HCC-240aa) to    2,3,3,3-tetrafluoro-1-propene (HFO-1234yf),-   2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) to    2,3,3,3-tetrafluoro-1-propene (HFO-1234yf),-   1,1,2,3 tetrachloro-1-propene (HCO-1230xa) to    2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);-   2,3,3,3 tetrachloro-1-propene (HCO-1230xf) to    2,3,3,3-tetrafluoro-1-propene (HFO-1234yf),-   1,1,1,2,3-pentachloropropane (HCC-240db) to    2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);-   1,1,2,2,3-pentachloropropane (HCC-240aa) to    2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);-   2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) to    2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);-   1,1,2,3 tetrachloro-1-propene (HCO-1230xa) to    2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);-   2,3,3,3 tetrachloro-1-propene (HCO-1230xf) to    2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf).

The fluorination reaction can be carried out with an HF molar ratiotypically from 3:1 to 150:1, at a contact time from 6 to 100 s and apressure from atmospheric pressure to 20 bars. The catalyst bedtemperature can be from 200 to 450° C.

In order to prevent a fast deactivation of the catalyst during thefluorination reaction, an oxidizing agent (such as oxygen or chlorine)can be added, for example at a rate of from 0.05 to 15 mol %, withrespect to the mixture of oxidizing agent plus chlorinated compound.

Catalyst

The fluorination catalyst used in the present invention can be supportedor unsupported.

It can be for example a catalyst based on a metal including a transitionmetal oxide or a derivative or halide or oxyhalide such a metal.Catalysts are e.g. FeCl₃, chromium oxyfluoride, chromium oxides (thatcan optionally be subject to fluorination treatments), chromiumfluorides, and mixtures thereof.

Other possible catalysts are the catalysts supported on carbon catalystsbased on antimony, catalysts based on aluminum (such as AlF₃ and Al₂O₃and oxyfluoride of alumina and aluminum fluoride).

Generally speaking, catalysts that can be used are chromium oxyfluoride,aluminum fluoride and oxyfluoride, and supported or unsupported catalystcontaining a metal such as Cr, Ni, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb, Mg.Reference can also be made to the disclosures of WO-A-2007/079431, atpage 7, lines 1-5 and 28-32, EP-A-939071, at paragraph [0022], WO2008/054781 at page 9 line 22 to page 10 line 34, WO 2008/040969 inclaim 1, all incorporated herein by reference.

A preferred embodiment uses a particular catalyst, which is a supportedmixed catalyst, containing both chromium and nickel. The molar ratioCr:Ni, with respect to the metallic element is generally between 0.5 and5, for example between 0.7 and 2, including close to 1. The catalyst maycontain from 0.5 to 20% chromium and 0.5 to 20% nickel in weight,preferably between 2 and 10% of each metal.

The metal in the catalyst is converted to metal derivatives duringactivation (or regeneration), including oxides, halides or halideoxides.

As far as supported catalysts are concerned, the catalyst support can beselected from materials known in the art to be compatible with HF athigher temperature and pressure. For example, fluorinated alumina,prefluorinated activated carbon, graphite or fluorinated graphite aresuitable catalyst supports.

The support is preferably made from aluminum. There are several possiblecarriers such as alumina, activated alumina or aluminum derivatives.These derivatives include aluminum halides and halide oxides ofaluminum, for example described in U.S. Pat. No. 4,902,838, or obtainedby the activation process.

Reference can be made to WO 2009/118628, and especially to thedisclosure of the catalyst from page 4, line 30 to page 7, line 16,which is incorporated herein by reference.

According to another embodiment, the process uses a high surface area Crbased catalyst which is preferably unsupported. A preferred catalyst isa high surface area unsupported chromium oxide catalyst.

The catalyst can optionally contain a low level of one or moreco-catalyst such as Co, Zn, Mn, Mg, V, Mo, Te, Nb, Sb, Ta, P and Nisalt. A preferred co-catalyst is nickel. Another preferred co-catalystis magnesium.

The preferred unsupported chromium catalyst can optionally contain lowlevels of one or more co-catalysts selected from cobalt, nickel, zinc ormanganese, prepared by processes known in the art, such as impregnation,mixed powder and the like.

The amount of co-catalyst, when present, can be varied between 1 to 10wt %, preferable between 1 to 5 wt %. The co-catalyst can be added tothe catalyst by processes known in the art such as adsorption from anaqueous or organic solution, followed by solvent evaporation. Thepreferred catalyst in this embodiment is pure chromium oxide with nickelor zinc as a co-catalyst. Alternatively the co-catalyst can bephysically mixed with the catalyst via grinding to produce an intimatemixture. An alternative catalyst is a mixed chromium/nickel catalystsupported on fluorinated alumina. U.S. Pat. No. 5,731,481, incorporatedherein by reference, discloses a method of preparation of thisalternative catalyst.

The catalyst, before activation, is subjected to a drying step,preferably comprises passing a drying gas, preferably nitrogen. Thedrying step can be carried out at a pressure of from atmosphericpressure up to 20 bars. The temperature of the catalyst during dryingstep can range from room temperature up to 400° C., preferably fromabout 100° C. to about 2 00° C. at a contact time from about 1 to 100 s,preferably from about 10 to 40 s, for approximately 1 to 50 hours,preferably between 5 to 20 hours.

After the drying step, the catalyst needs to be activated in order toreach the best level of catalyst activity.

Activation of the Catalyst

The present inventors have found that the activation of the abovecatalysts using an oxidizing agent-containing gas flow makes it possibleto significantly improve the efficiency of the fluorination process.

The activation process comprises activating the catalyst using oneactivating agent or two activating agents, in two steps or in a singlestep. One of the activating agents is an oxidizing agent, such as oxygenor an oxygen/nitrogen mixture or air or chlorine. The other activatingagent (if present) can be HF.

According to one embodiment, the activation process is a twostep-activation process, firstly with the oxidizing agent as a firstactivating agent, and then with HF as a second activating agent. First,the fresh catalyst is treated with the oxidizing agent. The temperatureduring this activation step can range from about 250 to about 500° C.,preferably from about 300 to about 400° C., with a contact time of fromabout 1 to about 200 s, for about 10 to about 200 hours. Then, thecatalyst is treated with HF. The temperature of the activation step withHF as an activating agent can range from about 100° C. to about 450° C.,preferably from about 200 to about 300° C., with a contact time of fromabout 1 to about 100 s, for about 1 to about 50 hours.

According to another embodiment, the activation process is a twostep-activation process, firstly with HF as a first activating agent,then with the oxidizing agent as a second activating agent. First thefresh catalyst is treated with HF. The temperature of the activationstep with HF as an activating agent can range from about 100 to about450° C., preferably from about 200 to about 300° C., with a contact timeof from about 1 to about 100 s, for about 1 to about 50 hours. Then, thecatalyst is treated with the oxidizing agent. The temperature of thisactivation step can range from about 250 to about 500° C., preferablyfrom about 300 to about 400° C., with a contact time of from about 1 toabout 200 s, for about 10 to about 200 hours.

According to another embodiment, the activation process is a twostep-activation process comprising an activation performed by runningthe fluorination reaction for an initial period of time, followed by theactivation with the oxidizing agent. The fluorination reaction can becarried out for about 6 to about 100 hours (for example for less than 50hours). The HF molar ratio during the fluorination reaction can rangefrom about 2 to about 40. The temperature of the activation step withthe oxidizing agent can range from about 250 to about 500° C.,preferably from about 300 to about 400° C., with a contact time of fromabout 1 to about 200 s, for about 10 to about 100 hours. Both steps canbe repeated, until the catalyst activity reaches its best level.

According to another embodiment, the activation process is a onestep-activation process with HF plus the oxidizing agent. The proportionof oxidizing agent in the mixture of HF and oxidizing agent can rangefrom about 2 to about 98 mol %. The temperature of the activation stepcan range from about 200 to about 450° C., with a contact time of fromabout 1 to about 200 s, for about 10 to about 200 hours.

According to another embodiment, the activation process is a onestep-activation process with only the oxidizing agent (without HF). Thetemperature of this activation step can range from about 250 to about500° C., preferably from about 300 to about 400° C., with a contact timeof from about 1 to about 200 s, for about 10 to about 300 hours.

The above activation processes can be carried out at a pressure of fromatmospheric pressure up to about 20 bars.

Regarding the above activation steps with HF, HF can be fed to thesystem with an inert gas such as nitrogen. The proportion of HF canrange from about 1 to about 100 mole % of the mixture.

Regarding the above activation steps with the oxidizing agent, theoxidizing agent can be fed to the system with an inert gas such asnitrogen. The proportion of oxygen or chlorine can then range from about1 to 100 mole % of the mixture.

The activation with the oxidizing agent-containing gas flow shouldpreferably be performed during at least 1 hour, preferably at least 2hours, more preferably at least 4 hours, even more preferably at least10 hours, most preferably at least 15 hours, at a temperature of from250 to 500° C., preferably from 300 to 400° C., more preferably from 350to 380° C. A temperature of approximately 370° C. is for exampleappropriate.

When the activation process comprises two steps (such as one with afirst activating agent and the other one with a second activatingagent), these steps can be repeated one, two or more times in analternated manner.

Regeneration of the Catalyst

The present inventors have also found that the efficiency of thefluorination reaction tends to decrease over time, but that it can beincreased again up to, and even above, the initial efficiency, bysubjecting the catalyst to regeneration stages wherein it is contactedwith an oxidizing agent-containing gas flow, in a similar way as duringthe initial activation stage.

According to one embodiment, each regeneration stage is a one-stepregeneration stage, which is carried out with oxygen or air or anoxygen/nitrogen mixture. The temperature during the regeneration stepcan range from about 250 to about 500° C., with a contact time of fromabout 1 to about 200 s, for about 10 to about 200 hours. Theregeneration step can be carried out at a pressure from atmosphericpressure to about 20 bars.

According to another embodiment, each regeneration stage is a one-stepregeneration stage, which is carried out with oxygen or air or anoxygen/nitrogen mixture and HF. The temperature during the regenerationstep can range from about 250 to about 500° C., with a contact time offrom about 1 to about 200 s, for about 10 to about 200 hours. Theregeneration step can be carried out at a pressure from atmosphericpressure to about 20 bars. The proportion of oxygen can range from about2 to about 98 mol % relative to the mixture of oxygen plus HF, and fromabout 20 to about 100 mol % relative to the mixture of oxygen plusnitrogen.

When reaction stages alternate with regeneration stages, the duration ofeach reaction stage can be from 50 to 2000 hours, preferably from 200 to1000 hours, and the duration of each regeneration stage can be from 10to 200 hours, preferably from 15 to 60 hours.

EXAMPLES

The following examples illustrate the invention without limiting it.

The equipment used comprises a tubular reactor of an internal diameterof 19 mm, made of INCONEL® alloy 600 surrounded by a tubular oven. It isalso equipped with pressure and temperature controllers. The reactants,preliminarily mixed owing to a static stirrer heater, are introduced ingaseous phase at the top of the reactor.

At the outlet of the reactor, a sample of the products of the reactionis taken, washed by a pre-column and analyzed online by a gas phasechromatography equipped with low polarity capillary column.

The analysis is carried out by gas phase chromatography using a columnCP Sil 8CB, dimensions 50 m×0.32 mm×5 μm and a column packed, 1%SP1000/carbopack B, 60/80 mesh 5 m of length. The programming oftemperature of the oven is the first one: 40° C. during 10 min thenslope of 10° C./min until 250° C. and the second one: 40° C. during 20min then slope of 10° C./min until 180° C.

Considering that xi is the initial amount of moles of raw material andxf the total final amount of moles of raw material, conversion (%) is:(xi−xf)/xi×100. Selectivity of a product is calculated by the ratiobetween the amount of moles recovered of this product and the totalamount of moles of products being the result of the reaction of the rawmaterial.

Some air is added in order to maintain the catalyst activity.

The contact time is defined as the ratio of the volume of catalyst bedon the total volume flow rate in the experimental conditions oftemperature and pressure. The molar ratio of HF is defined as the ratiobetween the molar flow rate of HF and the molar flow rate ofHFCO-1233xf. The molar ratio of oxygen is defined as the ratio betweenthe molar flow rate of oxygen and the molar flow rate of HFCO-1233xf.

Example 1: Fluorination of HFCO-1233xf, Activation with an InitialFluorination Reaction and then a Treatment with Air

Fluorination of HFCO-1233xf was performed in the reactor described abovewith 73 cm³ of Ni—Cr catalyst supported on AlF₃.

The catalyst used was a mixed nickel/chromium catalyst having an atomicratio Ni/Cr of 1, supported on alumina fluoride and prepared byimpregnating solutions of nickel and chromic anhydride (CrO₃). Afterimpregnation and drying, the solid was treated at a temperature between320° C. and 390° C. in the presence of a mixture of hydrofluoric acidand nitrogen (concentration by volume of 5 to 10% of this acid innitrogen).

The activation process comprised 1) catalyst fluorination performed byrunning the fluorination reaction during 46 hours at temperature of 340°C., a contact time of 6 and 12 s, a molar ratio of HF of 23 and 4 mol %of oxygen per mole of HFCO 1233xf; and 2) treatment under air at 370° C.and 1.5 L/h during 64 hours.

The reactor was continuously fed with 8.1 g/h of anhydrous HF and 2.2g/h of HFCO-1233xf at atmospheric pressure. Thus, the contact time was12.2 s, the molar ratio of HF was 24, and the reaction temperature was350° C. The amount of oxygen was 4 mol % with respect to the amount ofHFCO-1233xf. The conversion of HFCO 1233xf was 40.8%. Complete resultsare provided in Table 1 below.

Example 2: Fluorination of HFCO-1233xf, Catalyst of Example 1 Reusedafter Regeneration

With the same catalyst described in example 1, a regeneration step wasperformed with a treatment under air at 1.5 L/h, 370° C. during 16 h.Then, the reactor was continuously fed during 100 h with 4.4 g/h ofanhydrous HF and 1.2 g/h of HFCO-1233xf at atmospheric pressure. Thus,the contact time was 22.4 s, the molar ratio of HF was 24, and thereaction temperature was 350° C. The amount of oxygen was 9 mol % withrespect to the amount of HFCO-1233xf. The conversion was 64.4%, but adeactivation of the catalyst was observed over time and conversionfinally reached 33.4%. Complete results are provided in Table 1 below.

Example 3: Fluorination of HFCO-1233xf, Activation with an InitialFluorination Reaction and then a Treatment with Air

Fluorination of HFCO-1233xf was performed in the reactor described abovewith 73 cm³ of Ni—Cr catalyst supported on AlF₃ described in example 1.

The activation process comprised five cycles of: 1) catalystfluorination performed by running the fluorination reaction during 6 and30 hours in the conditions set forth below, followed by 2) a treatmentof the catalyst with air at 370° C. and 1.5 L/h during 16 and 64 hours.

For the purpose of the fluorination reaction, the reactor wascontinuously fed during 32 h with 3.4 g/h of anhydrous HF and 1 g/h ofHFCO-1233xf at atmospheric pressure. Thus, the contact time was 29 s,the molar ratio of HF was 22, and the reaction temperature was 350° C.The amount of oxygen was 7 to 8 mol % with respect to the amount ofHFCO-1233xf. The conversion was 69.7% and decreased over time until54.7%. Then, a regeneration step under 1.5 L/h of air at 370° C. during16 h was performed. After this step, an even higher conversion rate thanthe one initially observed (72.4%) was recovered.

Complete results are provided in Table 1 below.

Example 4 (Comparative Example): Fluorination of HFCO-1233xf, Activationwith HF Only

Fluorination of HFCO-1233xf was performed in the reactor described abovewith 73 cm³ of Ni—Cr catalyst supported on AlF₃ described in example 1.

After an activation of the catalyst with HF at atmospheric pressure and350° C., without treatment under air, the reactor was continuously fedwith 7.6 g/h of anhydrous HF and 2.2 g/h of HFCO-1233xf at atmosphericpressure. Thus, the contact time was 12.7 s, the molar ratio of HF was23, and the reaction temperature was 350° C. The amount of oxygen was 4mol % with respect to the amount of HFCO-1233xf. The conversion of HFCO1233xf was 9.1%.

TABLE 1 results Ex.1 Ex.2 Ex.3 Ex.4 Catalyst volume 73 73 73 73 73Catalyst 73 73 (cm³) regeneration Molar ratio of HF 24 24 24 22 22 22 23Contact time (s) 12.2 22.4 22.4 29 29 29 12.7 Molar ratio O₂/ 0.04 0.090.09 0.08 0.08 0.08 0.04 HFCO-1233xf Catalyst run time with 5.9 5.7 1017 33 34.5 1 HFCO-1233xf (h) Conversion 40.8 64.4 33.4 69.7 54.7 72.4 9.1(GC % area) Selectivity 66.4 63.9 63.8 65.7 64.6 65.1 63.7 in HFO-1234yfSelectivity 31.4 31.9 31.9 32.8 32.3 32.6 31.8 in HFC-245cb

Example 5 (Comparative Example): Fluorination of HFCO-1233xf withoutSpecific Activation

Fluorination of HFO-1233xf was performed in the reactor described abovewith 73 cm³ of Ni—Cr catalyst supported on AlF₃ described in example 1.

After loading of the catalyst in the reactor, the catalyst was driedwith nitrogen at 220° C. during 16 hours. Then the reactor temperaturewas brought to 350° C. and the reactor was continuously fed with 4.5 g/hof anhydrous HF and 1.2 g/h of HFCO-1233xf and air at atmosphericpressure and 350° C. The contact time was 22 s, and the HF MR was 24.The amount of oxygen was 9 mol % with respect to the amount ofHFCO-1233xf. The conversion of HFCO 1233xf reached 14.8% after 24 hoursof reaction.

Complete results are provided in Table 2 below.

Example 6: Fluorination of HFCO-1233xf, Activation with Air Only

Fluorination of HFCO-1233xf was performed in the reactor describedabove, with 73 cm³ of Ni—Cr catalyst supported on AlF₃ described inexample 1.

First, the catalyst was dried with nitrogen at 220° C. during 16 hours.Then, nitrogen feeding was stopped and air was introduced in the reactorduring 2 hours. After that, the oven temperature was brought to 370° C.and maintained at this temperature during 64 hours. After thisactivation of the catalyst, the oven temperature and air flow rate wereadjusted for the following experiment. The reactor was continuously fedwith 5.0 g/h of anhydrous HF and 1.1 g/h of HFCO-1233xf at atmosphericpressure. The contact time was 20 s, the HF MR was 30, and the reactiontemperature was 350° C. The amount of oxygen was 9 mol % with respect tothe amount of HFCO-1233xf. The conversion of HFCO 1233xf reached 18.5%after 22 hours of reaction.

Complete results are provided in Table 2 below.

Example 7: Fluorination of HFCO-1233xf, Activation with HF and then Air

Fluorination of HFCO-1233xf was performed in the reactor describedabove, with 73 cm³ of Ni—Cr catalyst supported on AlF₃ described inexample 1.

First, the catalyst was dried at atmospheric pressure with nitrogen at220° C. during 16 hours. Then, HF was introduced and maintained during 2hours. The oven temperature was brought to 350° C. an d maintained withHF during 3 hours. Next, HF was replaced by air at 1.5 L/hr and the oventemperature was brought to 370° C. and maintained during 16 hours. Afterthat, the oven temperature and the air flow rate were adjusted for thefollowing experiment and HF and HFCO-1233xf were introduced in thereactor. The reactor was continuously fed with 4.1 g/hr of anhydrous HFand 1.0 g/hr of HFCO-1233xf) at atmospheric pressure. The contact timewas 24 s, the HF MR was 26, and the reaction temperature was 350° C. Theamount of oxygen was 8 mol % with respect to the amount of HFCO-1233xf.The conversion of HFCO-1233xf reached 58.6% after 10 hours of reaction.

Complete results are provided in Table 2 below.

TABLE 2 results Ex. 5 Ex. 6 Ex. 7 Catalyst volume (cm³) 73 73 73 Molarratio of HF 24 30 26 Contact time (s) 22 20 24 Molar ratio 0.09 0.090.08 O₂/HFCO-1233xf Catalyst run time with HFCO- 24 22 10 1233xf (h)Conversion 14.8 18.5 58.6 (GC % area) Selectivity 98.6 97.3 97.3 inHFO-1234yf + HFC-245cb

1.-20. (canceled)
 21. A fluorination process, comprising: an activationstage comprising the following steps, in succession: i. reacting achlorinated compound selected from the group consisting of2-chloro-3,3,3-trifluoro-1-propene, 1,1,1,2,3-pentachloropropane,1,1,2,2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane,2,3,3,3-tetrachloro-1-propene and 1,1,2,3-tetrachloro-1-propene withhydrogen fluoride in gas phase in the presence of a chromium-basedfluorination catalyst, and ii. contacting the chromium-basedfluorination catalyst with a first oxidizing agent-containing gas flowcomprising an oxidizing agent and hydrogen fluoride; at least onereaction stage comprising reacting the chlorinated compound withhydrogen fluoride in gas phase in the presence of the fluorinationcatalyst, so as to produce a fluorinated compound; and at least oneregeneration stage comprising contacting the fluorination catalyst witha second oxidizing agent-containing gas flow.
 22. The process of claim21, wherein the first and/or second oxidizing agent-containing gas flowscomprise an oxygen-containing gas flow.
 23. The process of claim 21,wherein the activation stage and/or the at least one regeneration stagecomprise contacting the fluorination catalyst with the first and/orsecond oxidizing agent-containing gas flows for at least 2 hours. 24.The process of claim 21, wherein the second oxidizing agent-containinggas flow contains hydrogen fluoride in addition to the oxidizing agent,and wherein the proportion of oxidizing agent in the second oxidizingagent-containing gas flow is from 2 to 98 mol %, relative to the totalamount oxidizing agent and hydrogen fluoride.
 25. The process of claim21, wherein the second oxidizing agent-containing gas flow does notcontain hydrogen fluoride.
 26. The process of claim 21, wherein thefirst and/or second oxidizing agent-containing gas flow comprise air.27. The process of claim 21, wherein the activation stage and/or the atleast one regeneration stage comprise contacting the fluorinationcatalyst with a hydrogen fluoride gas flow, either: before contactingthe fluorination catalyst with the oxidizing agent-containing gas flow;or after contacting the fluorination catalyst with the oxidizingagent-containing gas flow.
 28. The process of claim 21, wherein thefirst and/or second oxidizing agent-containing gas flow is/are contactedwith the fluorination catalyst at a temperature of from 250 to 500° C.29. The process of claim 21, wherein the fluorinated compound is afluoroolefin.
 30. The process of claim 21, wherein the fluorinationcatalyst is a supported catalyst.
 31. The process of claim 21, whereinthe fluorination catalyst is an unsupported catalyst.
 32. The process ofclaim 21, wherein the fluorination catalyst further comprises aco-catalyst selected from the group consisting of Co, Zn, Mn, Mg, V, Mo,Te, Nb, Sb, Ta, P, Ni and mixtures thereof.
 33. The process of claim 32,wherein the co-catalyst is present in an amount from about 1-10 wt % ofsaid fluorination catalyst.
 34. The process of claim 21, wherein thefluorination catalyst is a mixed chromium/nickel catalyst.
 35. Theprocess of claim 21, wherein the chlorinated compound is2-chloro-3,3,3-trifluoro-1-propene.
 36. The process of claim 21, whereinthe at least one reaction stage is carried out at a pressure of from 1to 20 bars.
 37. The process of claim 21, wherein the at least onereaction stage is carried out at a temperature of from 200 to 450° C.38. The process of claim 21, wherein the contact time between hydrogenfluoride and the chlorinated compound during the at least one reactionstage is from 6 to 100 s.
 39. The process of claim 21, wherein the atleast one reaction stage is carried out in the presence of an oxidizingagent.